Coating compositions for moistureproofing by hot melt coating



Patented Jan. 4, 1949 COATING COMPOSITIONS FOR MOISTURE- PROOFIN G BY HOT MELT COATING Martin Salo, Rochester, N. Y., asslg'nor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application December 12, 1945,

Serial No. 634,628

This invention relates to a composition adapted to form moisture vaporproof coatings when applied in a molten condition to a surface. such as paper or cloth.

This application is a continuation-in-part of application Serial No. 527,153, now Patent No. 2,409,985.

Compositions of various kinds have been suggested for use in impartingmoisture vaporproof coatings to paper, cloth, or similar material. Some of these compositions give coatings which are soft or opaque or crease with breaking upon impact. In other cases, the moisture vaporproofing has been not as effective as desired. In most or all of the cases known, the composition for moisture vaporprooflng has been applied by means of a solution thereof in a volatile solvent.

This method involves the handling of organic solvents and solutions and for economical operation, the collecting of the vapors thereof and recovery of the same.

One object of my invention is to provide a novel composition which is of value as a nonblocking melt-coating composition to make possible the coating of surfaces without the use of a volatile solvent. Another object of my invention is to provide a practicable melt-coating composition which gives moisture vaporproof coatings which are hard, firm and flexible, giving surfaces which are clean, transparent and brilliant in character. A further object of my invention is to provide a cellulose ester composition which can be used for melt-coating purposes at restricted temperatures, such as ISO-200 C., but will be non-tacky at temperatures below 150 F. or 66 C. A still further object of my invention is to provide a moisture vaporproofing coating which will crease without breaking upon impact and will heatseal, forming a strong bond. Other objects of my invention will appear herein.

Claims. (Cl. 260-17) 2 tion possible or, in other words, the smallest proportions of plasticizer and blending agent which will give good fluidity and compatibility are preferably employed.

The cellulose esters which I have found to be suitable for use in compositions in accordance with my invention are butyric acid esters of cellulose having a butyryl content of at least 42% and a totalacylcontent of at least 50% and which .are either fully esterifled or have been hydrolyzed so that the esters have no more than about two hydroxyl groups per 24 cellulose carbon atoms. The cellulose esters employed should have a fundamental cuprammonium viscosity of less than centipoises and a viscosity within the range of 10-100 centipoises when one part of ester is dissolved in nine parts (by weight) of acetone at a temperature of 25 C. The fundamental cuprammonium viscosity is determined a by obtaining in centipoises the viscosity of a cuprammonium solution of the ester in which the cellulose of the ester is of 2%% concentration. The cellulose esters employed should be heat stable or, in other words, they should not darken or lose viscosity when moderately elevated tem- I have found that the following composition is eminently suited for melt-coating paper, cloth or other surfaces in molten condition which upon cooling and solidifying gives a high moisture vaporprooflng thereto.

Composition-At least 40% of a cellulose ester containing at least 42% butyryl and at least total acyl, 10-40% di-2-ethyl hexyl phthal; ate, -'7% of wax, such as paramn, and as the blending agent polyvinyl acetate in suflicient amount to render the wax compatible with the plasticized cellulose ester and to impart permanence to this composition. In order to obtain cellulose ester be present in the maximum proporperatures such as 15 0-200 C. are applied thereto. The cellulose esters which are employed in preparing my compositionsmay be prepared by.

reacting cellulosewith butyric anhydride, preferably after a pretreatment using little or no acetic acid, the acetyl, if any, being present in such small proportion in the esterification mass that the prescribed proportion of butyryl its present in the resulting product. The cellulose may be pretreated by the method described in Gardner Patent No. 2,113,301 preferably using therewith the dehydration method described in Malm Patent No. 2,315,973, or by the pretreatments described and claimed in Malm Patents Nos. 2,342,415 and 2,342,416, providing, of course, the acetic acid contained is kept to a minimum. Esterification of the cellulose with butyric anhydride and catalyst, such as by the methods described and claimed in Blanchard Patent No. 2,304,792, or Malm Patents Nos. 2,362,576 and 2,345,406, results in a high butyryl cellulose ester, particularly if the proportion of butyryl to the total acyl is kept sufliciently high in the esterification mass. If hydrolysis is employed, it is preferable that it only be for a suflicient time to reduce the sulfur content of the ester, as the substantially fully esterified esters are the most desirable for use in melt-coatingprocesses'in accordance with my invention. It is desirable that the esters employed have a char point of at least 260 C. If a high butyryl ester is available which does not have this char point, it should be stabilized, such as by the method described and claimed in Malm and Kirton Patent No. 2,250,201, or by the method described and claimed in Malm and Crane Patents Nos. 2,346,498 and 2,341,455, to a point where the ester does exhibit a char point of at least 260 C.

The cellulose esters employed in my compositions may be either simple esters i. e. cellulose butyrates, or mixed esters, i. e. cellulose acetate butyrates, cellulose propionate butyrates, or cellulos acetate propionate butyrates. A small part Of the butyryl in the esters may be replaced by propionyl or by fatty acid groups of .5-8 carbon atoms or even fatty acid groups of more than 8 carbon atoms although with the latter, the proportion should be quite small to avoid softness and stretchiness.

The plasticizer which I have found to be suitable in moisture vaporproofing melt-coating compositions in accordance with my invention is di-2- ethyl hexyl phthalate.

The plasticizer should be in a proportion of 10-40% of the composition. It is desirable that the least amount of plasticizer necessary to impart good fluidity to the composition be employed. With esters having a butyryl near to the tributyrate or a viscosity in the lower part of the viscosity range given, the amount of plasticizer need not be as great as with the higher viscosity cellulose esters or those with a butyryl content in the lower portion 01 the range given. If the plasticizer is employed in a greater proportion than that specified, the melt-coating composition, upon applying to a surface, solidifies slowly and yields a soft, non-rigid structure from which the wax has a tendency to crystallize out upon coating, giving a water vapor permeability higher than desired and also a poorappearance. A coating with a percentage of plasticizer above that specified also exhibits a tendency to be tacky at low temperatures, such as below 150 F. If plasticizer were employed in my composition in a proportion below 10%, it would be necessary to obtain good fluidity to employ cellulose esters of a lower viscosity than specified. The use such low viscosity esters would result in products of undesirable physical properties, such as brittleness. The above is offered as a guide as to the correct proportion of plasticizer to employ in a composition in accordance with my invention 'for the purpose to which the composition is to be adapted. Ordinarily, the suitable proportion of di-2-ethyl hexyl phthalate will be within the -4 0% range.

I have'ieund paraflln to be most satisfactory as a wax, for use in compositions in accordance with my invention. However, other waxes may be employed although there is some variation in their effectiveness. Beeswax and carnauba wax give good values for moisture vaporprooflng in accordance with my invention, as does also ceresin and Chinese wax. Waxes generally may be employed in compositions in accordance with my invention.

The wax should be present a proportion of at least in my compositions to resist the penetration of moisture and not more than 7%, as too great a proportion of wax tends to separate out and interfere with the brilliance and hardness of the coating therefrom.

The polyvinyl acetate blending agent should be unhydrolyzed polyvinyl acetate having a viscosity of 1 -10 centipoises. This viscosity is that of a solution in benzene of 86 g. of polyvinyl acetate per 1000 cc. of solution oi! 20 C. The polyvinyl acetate blending agent is necessary in the composition of my invention to cause'compatibility of the wax employed with the plasticized cellulose ester used and to avoid separating out of the wax ai'terv the composition has been applied as a melt coating to a surface which is to be protected. It is desirable that the poylvinyl acetate blending agent be employed in the minimum proportion necessary to impart compatibility and permanence to the composition in order to make possible the use of a high proportion of cellulose ester in the composition.

The proportion of polyvinyl acetate blending agent used in our composition should be sufilcient to render the wax compatible with the other ingredients of the composition. This depends to some extent upon the proportion of wax which is being employed. For instance, with the composition in which 1% of wax is used, a proportion of polyvinyl acetate such as one having a viscosity of 2.5 centipoises within the range of 5-20% will be most useful. With the use of a larger proportion of wax, such as 5%, a larger proportion of polyvinyl acetate is desirable, such as within the range of 15-40%.

The polyvinyl acetate 'used is selected as regards viscosity according to the other ingredients employed. For instance, when cellulose esters in the higher part of the viscosity range specified for those esters are employed, it is desirable to employ a polyvinyl acetate in the lower portion of the viscosity range specified herein. 0n the other hand, with the use of lower viscosity butyric acid'esters of cellulose, higher viscosity polyvinyl acetate may be employed. The criterion as to the composition is that the melt of that composition will be sufllciently fluid for coating purposes.

In preparing compositions in accordance with my invention, it is desirable that the wax, the blending agent and the plasticizer first be thoroughly mixed together at an elevated temperature, such as -180 C. After these materials have been melted together, the cellulose ester may be slowly introduced into the mixture with stirring. A smooth, homogeneous melt may be obtained thereby which is eminently suitable for melt-coating operations. It is desirable that the melt exhibit a viscosity between 10,000 and 50,000 centipoises for the best results in the meltcoating operation. Where the properties of the coating are important, it is desirable to have as large a proportion of cellulose ester in the com position as possible providing the fluidity, compatibility, and moistureproofing properties of the composition are sufilcient. The ultimate composition desired for this purpose will vary depending upon the characteristics regarded as most important by the individual operator.

If desired, after a homogeneous melt of the ingredients of my composition is obtained, the mixture may be led directly to the coating machine or it may be broken up into granules so that it may be stored and used when convenient. The granules may be meltedwhen desired for coating in suitable heated mixing equipment or a heated piston or a worm gear extruder and fed into a melt-coating machine, particularly one which operates in a continuous manner. Various types of apparatus may be employed to coat the melt-coating composition onto the surface of a material to support the vaporproof coating. The coating may be applied onto its support by any one of four different coating methods. namely,

the knife, the roll, the casting and extrusion methods. The roll-coating method involving a pick-up and applicator roll seems most practical at the present time. The roll-coating type'oi' machine can be adapted to a squeeze or calender method of coating by passing the cloth or paper between the two coating rolls, rotating in the direction of the material. With this method, it is possible to coat both sides simultaneously if the melt is provided for both the top and bottom of the paper. After coating, the materialgmay then pass through a smoothing apparatus such as depends upon the use of a heated bar of suitable design. Upon cooling, the material will be found to have a surface of good clarity and color. The various methods of applying hot-melt compositions are shown in" the art and need not be repeatedhcre. For the coating of articles which cannot ,be put through such apparatus, such articles as electrical equipment, tools, packaged merchandise and the like, a coating maybe applied thereto by dipping the article in the composition in a molten condition.

Coatings 'of compositions in accordance with my invention have been found to give moisture vapor permeabilities at 104 F. and 80% relative meability at 104 F. and 80 relative humidity of .054 mg. per square centimeter per hour.

Example 3.-The same procedure was employed as in the preceding examples using .the following proportions of materials: 51.8 parts of cellulose acetate butyrate, 22.2 parts of di-2-ethyl hexyl phthalate, 25 parts of unhydrolyzed polyvinyl acetate, and one part of paraflin. The water-vapor permeability of the coated glassine paper obtained was .036.

Example 4.A melt-coating composition was preparedby mixing together 66 parts of cellulose acetate butyrate containing 46.7% of butyryl and 6.8% of acetyl and having a. viscosity of 82 centipoises in a 10% solution in acetone, parts of di-2-ethyl hexyl phthalate, 13 parts of unhydrolyzed polyvinyl acetate, and one part of paraflin at "a temperature of 160-480 C. This mixture was humidity of .02 to .04 mg. per square centimeter per hour in coatings of a thickness of .0005 to .001 inch on glassine paper, thus comparing with the best moisture vaporpr'oof coatings coated out from solvents.

Some typical compositions which are very suitable for melt-coating using cellulose acetate butyrate having a butyryl content of 50% and a viscosity in 10% solution in acetone of 100 centrpoises, polyvinyl acetate having a viscosity of 2.5 C. P. S. as the blending agent and 1% of parafiln wax are as follows:

Dl-Q-Ethyl Cellulose Polyvinyl Hexyl Ester; Phthalate Acetate Percent Percent Percent 66 19 14 64 23 12 68 13 18 70 19 10 of cli-2-ethyl hexyl phthalate, 15.parts of unhy drolyzed polyvinyl acetate and one part of paraifin at a temperature of 160-180 C. This mixture was stirred for four hours at 160-180 C. and was then coated onto both sides of glassine paper on a Waldren type hot-melt-coating machine. A flexible, brilliant glassine paper was obtained having a water-vapor permeability of'.031. This compares will with moisture-proofed Cellophane which was used as a check and exhibited a watervapor permeability of .024.

Example 2.The preceding example was repeated except that the materials employed were mixed in the following proportions: 55.3 parts of cellulose acetate butyrate, 23.7 parts oi. di-2 ethyl hexylv phthalate, 20 parts of unhydrolyzed polyvinyl acetate, and one part of paraflin. The coated glassine paper obtained had a water-vapor perstirred for four hours at 160180 C.-and was then coated onto glassine paper on a Waldren type hot melt-coating machine. The resulting paper was tested for water-vapor permeability, this value being .037 mg. per square centimeter per hour. Example 5.--The preceding example was repeated except that the materials were employed in the following proportions: 59 parts of cellulose acetate butyrate, 20 parts of di-2-ethyl hexyl phthalat'e, 20 parts of unhydrolyzed polyvinyl acetate, and one part of paraflin. The coated glassine paperobtained had a water-vapor permeability of .051 mg. per square centimeter per hour.

Ordinarily, compositions in accordance with my invention give the most desirable coatings if the coatings'are set quickly, such as by rapidly leading the coated material from the coating point to a region of lower temperature. However, I have found that even in cases where the setting 'takesplace slowly or some opaqueness is present that the low water-vapor permeability of the coating is still present.

My compositions are particularly adapted for coating sheet materials, such as cloth, paper, glassine, sheet metals or foils or the like. If desired, however, articles may be clipped in the composition in molten condition to give a moisture vaporproof coating thereon. It is preferred in the majority of cases thatthe paper or other material being coated be of at least moderate strength so as to avoid any danger of breakage in the coating operation. Paper or cloth coated as described herein may be employed for wrapping'materials in which either loss of moisture from the contents of the package or the taking on of moisture is to be prevented. My invention is only limited by the scope of the appended .range of 10-40% to impart good fluidity to the composition at 150200 C., V2-7% Of a Wa and unhydrolyzed polyvinyl acetate having a viscosity of -10 centipoises, determined in solution in benzene of 86 g. polyvinyl acetate per 1000 cc. of solution at 20 C., sumcient in amount within the range -40% to render the wax permanently compatible with the composition.

2. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability essentially consisting of at least 40% of a heat stable butyric acid ester or cellulose having a butyryl content of at least 42%, a total acyl content of at least 50%, a cuprammonium viscosity of less than centipoises, a viscosity in 10% acetone solution at 25 C. of 10 200 centipoises, and not more than 2 hy.-, droxyl groups per 24 cellulose carbon atoms. sufilcient di-2-ethyl hexyl phthalate within the range of 10-40% to impart good fluidity to the composition at 150-200 C., V -7% paraflin wax, and sufllcient unhydrolyzed polyvinyl acetate having a viscosity of -10 centipoises, determined in solution in benzene 01 86 g. polyvinyl acetate per 1000 cc. of solutionvat 0., sumcient in amount within the range 5-40% torender the paraflln wax permanently compatible with the composition.

3. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability essentially consisting of at least 40% of a heat stable cellulose acetate butyrate having a butyryl content 01 approximately 49% and an acetyl content of approximately 6%, a cuprammonium viscosity of less than 10 centipulses, a viscosity in 10% acetone solution of C. of approximately 27 centipoises, and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, sufilcient di-2-ethyl hexyl phthalate within the range of 10-40% to impart good fluidity to the composition at 150-200 C., %-7% of wax and unhydrolyzed polyvinyl acetate having a viscosity of -10 centipoises, determined in solution in benzene of 86 g. polyvinyl acetate per 1000 cc. of solution at 20 C., sumcient in amount within the range 5-40% to render the wax permanently compatible with the composition.

4. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability essentially consisting of app mately 60 arts of a heat stable cellulose acetate butyrate having a butyryl content of at least 42% and a total acyl content of at least 50% a, cuprammonium viscosity of less than 10 centipoises, an acetone viscosityin 10% solution at 25 C. of 10-200 centipoises, and not more than two hydroxyl groups per 24 cellulose carbon atoms, approximately 25 parts of di-2-ethyl hexyl phthalate, one part of paraflin. and 15 parts of unhydrolyzed polyvinyl acetate 01 V centipoises viscosity determined in solution in benzene of 86 g. polyvinyl acetate per 1000 cc. of solution at 20 C.

5. Glassine paper having a melt coating thereon, which coating essentially consists oi at least 40% of a heat stable butyric acid ester of cellulose having a butyryl content of at least 42% and a total acyl content of at least a cuprammonium viscosity of less than 10 centipoises, an acetone viscosity in 10% solution at 25 C. of 10-200 centipoises and not more than two hydroxyl groups per 24 cellulose carbon atoms, 10- 40% of di-2-ethyl hexyl' phthalate, /-7% of wax and unhydrolyzed polyvinyl acetate --l0 centipoises viscosity determined in solution in benzene of 86 g. polyvinyl acetate per 1000 cc. of solution at 20 C., sumcient in amount within the range of 5-40% to render the wax permancntly compatible with the composition.

MARTIN SALO.

REFERENCES CITED The following references are of record in the 

